CN114317970A - Recovery method of waste lithium cobalt oxide battery - Google Patents

Recovery method of waste lithium cobalt oxide battery Download PDF

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Publication number
CN114317970A
CN114317970A CN202111445436.8A CN202111445436A CN114317970A CN 114317970 A CN114317970 A CN 114317970A CN 202111445436 A CN202111445436 A CN 202111445436A CN 114317970 A CN114317970 A CN 114317970A
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Prior art keywords
acid
leaching
column
cobalt
shaped container
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CN202111445436.8A
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CN114317970B (en
Inventor
钟应声
余海军
谢英豪
李爱霞
李波
李长东
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Yichang Bangpu Times New Energy Co ltd
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Yichang Bangpu Times New Energy Co ltd
Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202111445436.8A priority Critical patent/CN114317970B/en
Publication of CN114317970A publication Critical patent/CN114317970A/en
Priority to ES202390158A priority patent/ES2957175A2/en
Priority to HU2300357A priority patent/HUP2300357A1/en
Priority to MA62704A priority patent/MA62704A1/en
Priority to DE112022000893.8T priority patent/DE112022000893T5/en
Priority to PCT/CN2022/114550 priority patent/WO2023098167A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/42—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation
    • C01F7/428—Preparation of aluminium oxide or hydroxide from metallic aluminium, e.g. by oxidation by oxidation in an aqueous solution
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
    • C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
    • C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/40—Mixtures
    • C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Abstract

The invention discloses a method for recycling waste lithium cobalt oxide batteries, which comprises the steps of loading black powder of the lithium cobalt oxide batteries into a column-shaped container, adding first acid into the column-shaped container for hot leaching until the solid in the column-shaped container is not reduced any more, obtaining first leaching liquid and leaching residues, wherein the first acid is weak acid, the bottom of the column-shaped container is provided with a filtering structure, adding second acid into the column-shaped container filled with the leaching residues for hot leaching until the solid in the column-shaped container is not reduced any more, obtaining second leaching liquid and graphite, and the second acid is strong acid. According to the invention, the leaching mode of the battery black powder is changed, and the acid-resistant column container is selected to be matched with the first acid and the second acid for selective hot leaching for leaching, so that on one hand, the consumption of inorganic strong acid can be reduced, the emission of strong acid gas can be reduced, green low-carbon hot leaching of the black powder is realized, and on the other hand, the acid consumption can be saved by adopting the column container with a filtering structure.

Description

Recovery method of waste lithium cobalt oxide battery
Technical Field
The invention belongs to the technical field of lithium ion battery recovery, and particularly relates to a recovery method of waste lithium cobalt oxide batteries.
Background
The lithium ion battery (power battery) for automobile power has the advantages of high working voltage, high energy density, low cost and the like, has long cycle life, and is widely applied to the fields of transportation, electric energy storage and the like. With the life of LIBs coming, it will be inevitable to produce a large number of used LIBs. The waste power battery contains precious metal resources such as lithium, cobalt and the like and harmful organic matters, and the environment can be polluted without reasonable treatment. At present, the waste power battery is recycled, the problem that the existing resource quantity cannot meet the requirement of rapid growth can be solved, and the environment and the resources can be saved. Therefore, the development of a recycling technology of waste power batteries is urgent.
The existing waste lithium ion battery recovery strategy mainly comprises wet method and fire method recovery. With wet recovery being more widespread. It is suitable for industrial use because of its high recovery rate and normal temperature reaction. Currently, the popular hydrometallurgical processes include pretreatment, leaching and regeneration processes. The key to the pretreatment is the effective separation of the waste material from the aluminum foil in the waste electrode plate. This common separation method can be classified into organic solvent dissolution, thermal decomposition, alkaline leaching and acid leaching. The organic solvent dissolving method can realize short operation time of dissolving polyvinylidene fluoride (PVDF), but has the defects of organic toxicity, easy volatilization, high price and the like. The method is used to dissolve aluminum foil to separate cathode materials, which also easily damages the equipment. The thermal decomposition method can be used for decomposing PVDF, but has the advantages of high energy consumption, low cost and harmful gas release. The alkaline leaching for dissolving the aluminum generally has the problems of incomplete aluminum removal, cobalt loss, complicated recovery steps and easy residue in the solution. The inorganic acid is used for leaching and dissolving aluminum and copper, less substances which are selectively dissolved exist, and the positive electrode active material, the aluminum and the copper are dissolved, so that the aluminum and the copper need to be further recovered. In addition, in wet recovery, the cobalt is recovered by the procedures of precipitation, impurity removal, extraction, back extraction, crystallization and the like, the recovery process is long, and meanwhile, the used chemical reagents are various, so that the subsequent treatment of the solution is troublesome, and the development of a clean and efficient recovery method is of great significance.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a method for recovering waste lithium cobalt oxide batteries.
According to one aspect of the invention, the recovery method of the waste lithium cobalt oxide battery is provided, and comprises the following steps:
s1: filling black cobalt acid lithium battery powder into a column-shaped container, adding a first acid into the column-shaped container for hot leaching until the solid in the column-shaped container is not reduced any more, so as to obtain a first leaching solution and leaching residues, wherein the first acid is a weak acid, and the bottom of the column-shaped container is provided with a filtering structure;
s2: and adding a second acid into the column-shaped container filled with the leaching residues for hot leaching until the solid in the column-shaped container is not reduced any more, so as to obtain a second leaching solution and graphite, wherein the second acid is a strong acid.
In some embodiments of the present invention, in step S1, the lithium cobaltate battery black powder is obtained by the following process: splitting a waste lithium cobaltate battery pack into monomers, detecting the voltage of the monomers, classifying the monomers into low-voltage monomers and high-voltage monomers, discharging, pyrolyzing and crushing the low-voltage monomers, and screening to remove copper aluminum foils and diaphragms to obtain the lithium cobaltate battery black powder. Preferably, the discharging is to soak the low-voltage monomer in the tap water discharging liquid for 2 to 10 days. Preferably, the voltage of the low-voltage monomer is less than 2.5V, and the voltage of the high-voltage monomer is more than or equal to 2.5V. Preferably, the pyrolysis is carried out by oxygen-introducing pyrolysis at the temperature of 400-900 ℃ for 4-12 h.
In some embodiments of the invention, the high voltage cells are assembled into a battery pack as a heating power source. Preferably, the manner of assembling the battery pack is as follows: f high-voltage monomers are connected in series to obtain a single string TiV battery, then r strings TiV batteries are connected in parallel and are connected with a battery protection plate and a protection film for fixing to obtain TiV battery pack. Further, said T1V is the voltage of the 1 st high-voltage monomer, and so on, TfV is the f-th high-voltage cell voltage, Ti＝∑(T1+T2+T3+...+Tf)，2.5f≤TiF is not more than 4.2f, f is more than 1 and not more than 50, r is not less than 0 and not more than 50, and f and r are natural numbers.
In some embodiments of the present invention, in step S1, the filtering structure is a gravity type filter or a pressure type filter, and the filtering structure can only filter liquid.
In some embodiments of the present invention, the method further comprises a step of preparing cobalt oxalate from the first leaching solution: adding alkali into the first leaching solution to adjust the pH value, separating out aluminum hydroxide precipitate, adding the second acid to adjust the pH value to 3.0-4.5, adding a co-extractant to perform extraction, separating out a cobalt-containing phase, adding the second acid into the cobalt-containing phase to perform back extraction, separating to obtain a back extraction solution, adding an oxalic acid source into the back extraction solution, and performing solid-liquid separation to obtain the cobalt oxalate. Preferably, the pH of the first leaching solution is adjusted to 4.0-6.5 by adding alkali.
In some embodiments of the invention, in step S1, the solid-to-liquid ratio (w/v) of the lithium cobaltate battery black powder to the first acid is (1-2): (5-20).
In some embodiments of the present invention, in step S2, the second leachate is first added with aluminum powder to separate copper sponge, and then added with alkali to adjust the pH to 4.0-6.5 to separate aluminum hydroxide. Preferably, the adding amount of the aluminum powder is 0.25-0.40 of the mass of the copper in the second leaching solution. Preferably, the base consists of sodium hydroxide and 1-20 wt% of at least one of sodium carbonate, ammonium carbonate or ammonium bicarbonate.
In some embodiments of the invention, in step S1, the first acid is at least one of formic acid, acetic acid, or benzoic acid; the acid content of the first acid is 0.1-35 wt%.
In some embodiments of the invention, the temperature of the first acid is 35-80 ℃ in step S1; the first acid also contains sodium thiosulfate, and the content of the sodium thiosulfate is 0.1-12 wt%. Preferably, the first acid is electrically heated by connecting the battery pack with a heater. The first acid is weak acid, the ion radius of the weak acid radical is large, and H ionized from the weak acid+The activity of (a) is somewhat hindered, so that the leaching rate is increased by means of heating and addition of sodium thiosulfate.
In some embodiments of the present invention, in step S1, the first leachate may be mixed with the first acid or used alone for the hot leaching of step S1.
In some embodiments of the invention, in step S2, the second acid is at least one of hydrochloric acid, phosphoric acid, sulfuric acid, or nitric acid; the concentration of the second acid is 0.01-0.2 mol/L; the temperature of the second acid is 35-80 ℃. Preferably, the second acid is electrically heated by the battery pack connecting heater. The recovered high-voltage monomer is prepared into a power supply for heating the first acid and the second acid, the residual electric energy of the waste battery is used for the hot leaching of the black powder, and the waste battery is reused, so that the cost of the hot leaching of the black powder can be reduced.
In some embodiments of the present invention, in step S2, in the thermal leaching process, the solid-to-liquid ratio (w/v) of the leaching residue to the second acid is (1-2): (0.2-20).
In some embodiments of the present invention, the synergistic agent is prepared from (15-50): (30-85) and cyclohexane, wherein the extracting agent is prepared from the following components in a volume ratio of (1-4): (1-10) dialkylphosphinic acid and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester. Preferably, the temperature of the extraction is 45-75 ℃. The novel co-extractant prepared from dialkyl hypophosphorous acid, 2-ethylhexyl phosphate mono-2-ethylhexyl ester and cyclohexane co-extractant is used for extracting cobalt in the first leaching solution, the purity of the cobalt oxalate obtained by extraction and oxalic acid addition completely reaches the standard that the cobalt content is more than 31.5%, the copper content is less than 0.0008%, the aluminum content is less than 0.001%, the sodium content is less than 0.001%, and the iron content is less than 0.001%, and the purity is high, so that the requirement of battery-grade cobalt oxalate is met.
In some embodiments of the invention, the oxalic acid source is at least one of oxalic acid, ammonium oxalate or sodium oxalate.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. by changing the leaching mode of the battery black powder, an acid-resistant column-shaped container is creatively selected to be matched with a first acid and a second acid for selective hot leaching for leaching, the first acid is weak acid, the first acid is adopted for selective hot leaching of the anode active substance lithium cobaltate in the black powder, only a small part of aluminum and copper are leached in the first leaching solution, the second acid is added into the column-shaped container for leaching copper and aluminum, the rest is graphite insoluble in acid, and further, the aluminum powder can be used for reducing and recovering copper, adjusting pH to precipitate aluminum and recovering aluminum.
2. The selective hot leaching method can reduce the consumption of inorganic strong acid, reduce the emission of strong acid gas and perform green low-carbon hot leaching on black powder, and can save the acid consumption by adopting the cylindrical container with the filtering structure.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic view of thermal leaching in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
A recovery method of waste lithium cobalt oxide batteries is disclosed, referring to FIG. 1, and the specific process is as follows:
1. and (4) classification: splitting a waste power battery pack (group) into monomers, detecting according to the residual output voltage of the monomers, measuring and classifying to obtain a first waste power battery (less than 2.5V) and a second waste power battery (more than or equal to 2.5V), sending the first waste power battery into a bucket containing tap water discharge liquid, soaking for 5d, discharging, then sending to a kiln at 840 ℃ for pyrolysis for about 7.5h, cooling, crushing, screening to remove copper aluminum foil and diaphragm to obtain black powder; 5 second waste power battery monomers are connected in series to obtain a single-string 16V battery pack, 3 the second waste power battery monomers are connected in series and in parallel, a circuit protection plate is connected, and a fire-resistant film is sleeved on the circuit protection plate to obtain the 5-string 3-parallel 16V battery pack which is used as a heating power supply. The main components of the black powder were measured as shown in table 1.
TABLE 1
Composition of Cobalt Lithium ion source Aluminium Copper (Cu) Graphite
Content% 36.4 4.3 3.1 7.8 13.6
2. Selective hot leaching: 400g of black powder is put into a long cylinder (the bottom is provided with a filter screen) decorated by acid-proof polytetrafluoroethylene, a 16V battery pack is connected with a heater to heat acetic acid to about 58 ℃, 15.4 wt% of acetic acid (containing 4.7 wt% of sodium thiosulfate) is poured into the long cylinder, hot pouring and soaking are carried out under stirring, the hot pouring and soaking are continued until the solid in the container is not reduced, 6.8L of acetic acid is consumed totally, 6.6L of first leaching solution under the container is obtained through filtering by the filter screen (the components of the first leaching solution are measured to be 19.3g/L of cobalt, 2.4g/L of lithium, 0.16g/L of aluminum and 0.20g/L of copper, the leaching rate of cobalt is calculated to be 87.5%, the leaching rate of aluminum is 8.5% and the leaching rate of copper is 4.2%), slag in the container is leached, the 16V battery pack is connected with the heater to heat sulfuric acid to about 68 ℃, 7.7 wt% of sulfuric acid is added into the slag to continue hot pouring and soaking and leaching the slag in the container is not reduced, consuming 0.8L of sulfuric acid in total, filtering the solution by a filter screen to obtain graphite and a second leaching solution, adding 9g of aluminum powder into the second leaching solution, separating to obtain 29.6g of sponge copper, adding 0.15mol/L of sodium hydroxide (containing 10.6 wt% of sodium carbonate) to regulate the pH value of the second leaching solution to 6.1, and performing filter pressing to obtain 59.3g of aluminum hydroxide.
3. Extracting and preparing cobalt oxalate: adding 0.15mol/L sodium hydroxide (containing 10.1 wt% of sodium carbonate) into the first leaching solution to control the pH value to be 6.3, separating to obtain 3.9g of aluminum hydroxide precipitate, adding 14.1 wt% of sulfuric acid to control the pH value to be 3.7, adding a novel extraction accelerator (dialkyl hypophosphorous acid: 2-ethylhexyl phosphate mono-2-ethylhexyl: cyclohexane 1.5: 3.5: 10, mixing, adding 0.15mol/L sodium hydroxide, saponifying by 40%), mixing, extracting, oscillating at 60 ℃ for 30min in an oscillating box, standing for 12min, separating to obtain a cobalt-containing phase, adding 7.1 wt% of sulfuric acid for back extraction, separating to obtain a back extraction solution, adding sodium oxalate into the back extraction solution until no precipitate is generated, performing solid-liquid separation, washing solids, and drying to obtain 323g of battery-grade light red cobalt oxalate.
Example 2
A method for recovering waste lithium cobalt oxide batteries comprises the following specific processes:
1. and (4) classification: splitting a waste power battery pack (group) into monomers, detecting according to the residual output voltage of the monomers, measuring and classifying to obtain a first waste power battery (less than 2.5V) and a second waste power battery (more than or equal to 2.5V), sending the first waste power battery into a bucket containing tap water discharge liquid, soaking for 5d, discharging, then sending to a kiln at 840 ℃ for pyrolysis for about 7.5h, cooling, crushing, screening to remove copper aluminum foil and diaphragm to obtain black powder; 5 second waste power battery monomers are connected in series to obtain a single-string 16V battery pack, 3 the second waste power battery monomers are connected in series and in parallel, a circuit protection plate is connected, and a fire-resistant film is sleeved on the circuit protection plate to obtain the 5-string 3-parallel 16V battery pack which is used as a heating power supply. The main components of the black powder were measured as shown in table 2.
TABLE 2
Composition of Cobalt Lithium ion source Aluminium Copper (Cu) Graphite
Content% 36.4 4.3 3.1 7.8 13.6
2. Selective hot leaching: 400g of black powder is put into a long cylinder (the bottom is provided with a filter screen) decorated by acid-proof polytetrafluoroethylene, a 16V battery pack is connected with a heater to heat acetic acid to about 68 ℃, 15.4 wt% of acetic acid (containing 4.7 wt% of sodium thiosulfate) is poured into the long cylinder, hot pouring and soaking are carried out under stirring, 5.3L of acetic acid is continuously poured and soaked until the solid in the container is not reduced, 5.1L of the acetic acid is consumed, a first leaching solution under the container is obtained by filtering through the filter screen (the components of the first leaching solution are measured to be 26.3g/L of cobalt, 3.2g/L of lithium, 0.24g/L of aluminum and 0.53g/L of copper, the leaching rate of the cobalt is calculated to be 92.1%, the leaching rate of the aluminum is 9.8%, the leaching rate of the copper is 8.6%), slag in the container is leached, the 16V battery pack is connected with the heater to heat sulfuric acid to about 73 ℃, 7.7 wt% of sulfuric acid is added into the slag to continue hot pouring and leaching until the slag is not reduced, consuming 0.7L of sulfuric acid, filtering by a filter screen to obtain graphite and a second leaching solution, adding 9g of aluminum powder into the second leaching solution, separating to obtain sponge copper, adding 0.15mol/L of sodium hydroxide (containing 10.1 wt% of sodium carbonate) to regulate the pH value of the second leaching solution to 6.1, and performing filter pressing to obtain 59.6g of aluminum hydroxide.
3. Extracting and preparing cobalt oxalate: adding 0.10mol/L sodium hydroxide (containing 5.1 wt% of sodium carbonate) into the first leaching solution to control the pH value to be 6.5, separating to obtain precipitate 4.1g of aluminum hydroxide, adding 14.1 wt% of sulfuric acid to control the pH value to be 3.8, adding a novel synergistic agent (dialkyl hypophosphorous acid: 2-ethylhexyl phosphate mono-2-ethylhexyl ester: cyclohexane 1.5: 3: 10, mixing, adding 0.15mol/L sodium hydroxide, saponifying for 40%), extracting, mixing, oscillating at 60 ℃ in an oscillating box for 30min, standing for 12min, separating to obtain a cobalt-containing phase, adding 7.1 wt% of sulfuric acid, back-extracting, separating to obtain a back-extraction solution, adding sodium oxalate into the back-extraction solution until no precipitate is generated, performing solid-liquid separation, performing solid washing, and drying to obtain 326g battery-grade pale red cobalt oxalate.
Example 3
A method for recovering waste lithium cobalt oxide batteries comprises the following specific processes:
1. and (4) classification: splitting a waste power battery pack (group) into monomers, detecting according to the residual output voltage of the monomers, measuring and classifying to obtain a first waste power battery (less than 2.5V) and a second waste power battery (more than or equal to 2.5V), conveying the first waste power battery into a bucket containing tap water discharge liquid, soaking for 5d, discharging, conveying to a kiln for pyrolysis at 650 ℃ for about 12h, cooling, crushing, screening to remove copper aluminum foil and diaphragm to obtain black powder; 5 second waste power battery monomers are connected in series to obtain a single-string 16V battery pack, 3 the second waste power battery monomers are connected in series and in parallel, a circuit protection plate is connected, and a fire-resistant film is sleeved on the circuit protection plate to obtain the 5-string 3-parallel 16V battery pack which is used as a heating power supply. The main components of the black powder were measured as shown in table 3.
TABLE 3
Composition of Cobalt Lithium ion source Aluminium Copper (Cu) Graphite
Content% 36.6 4.4 3.2 7.7 13.3
2. Selective hot leaching: 400g of black powder is put into a long cylinder (the bottom is provided with a filter screen) decorated by acid-proof polytetrafluoroethylene, a 16V battery pack is connected with a heater to heat acetic acid to about 74 ℃, 15.4 wt% of acetic acid (containing 4.7 wt% of sodium thiosulfate) is poured into the long cylinder, hot pouring and soaking are carried out under stirring, the hot pouring and soaking are continued until the solid in the container is not reduced, 4.8L of acetic acid is consumed totally, 4.6L of first leaching solution under the container is obtained through filtering by the filter screen (the components of the first leaching solution are measured to be 29.5g/L of cobalt, 3.6g/L of lithium, 0.29g/L of aluminum and 0.43g/L of copper, the leaching rate of cobalt is calculated to be 92.7%, the leaching rate of aluminum is 10.4% and the leaching rate of copper is 6.5%), slag in the container is leached, the 16V battery pack is connected with the heater to heat sulfuric acid to about 78 ℃, 7.7 wt% of sulfuric acid is added into the slag to continue hot pouring and leaching and reducing the slag in the container, consuming 0.6L of sulfuric acid, filtering by a filter screen to obtain graphite and a second leaching solution, adding 10g of aluminum powder into the second leaching solution, separating to obtain sponge copper, adding 0.15mol/L of sodium hydroxide (containing 10.1 wt% of sodium carbonate) to regulate the pH value of the second leaching solution to 6.3, and performing filter pressing to obtain 61.1g of aluminum hydroxide.
3. Extracting and preparing cobalt oxalate: adding 0.15mol/L sodium hydroxide (containing 10.1 wt% of sodium carbonate) into the first leaching solution to control the pH value to be 6.3, separating to obtain precipitate 4.3g of aluminum hydroxide, adding 14.1 wt% of sulfuric acid to control the pH value to be 3.9, adding a novel synergistic agent (dialkyl hypophosphorous acid: 2-ethylhexyl phosphate mono-2-ethylhexyl ester: cyclohexane 1.5: 3: 8, mixing, adding 0.15mol/L sodium hydroxide, saponifying for 45%), extracting, mixing, oscillating at 60 ℃ in an oscillating box for 30min, standing for 12min, separating to obtain a cobalt-containing phase, adding 7.1 wt% of sulfuric acid, back-extracting, separating to obtain a back-extraction solution, adding sodium oxalate into the back-extraction solution until no precipitate is generated, performing solid-liquid separation, washing solids, and drying to obtain 332g of battery-grade pale red cobalt oxalate.
Example 4
A method for recovering waste lithium cobalt oxide batteries comprises the following specific processes:
1. and (4) classification: splitting a waste power battery pack (group) into monomers, detecting according to the residual output voltage of the monomers, measuring and classifying to obtain a first waste power battery (less than 2.5V) and a second waste power battery (more than or equal to 2.5V), conveying the first waste power battery into a bucket containing tap water discharge liquid, soaking for 5d, discharging, conveying to a kiln for pyrolysis at 650 ℃ for about 12h, cooling, crushing, screening to remove copper aluminum foil and diaphragm to obtain black powder; and connecting 6 second waste power battery monomers in series to obtain a single-string 19V battery pack, connecting 4 second waste power battery monomers in series and parallel, connecting a circuit protection plate, and sleeving a fire-resistant film to obtain 6-string 4-parallel 19V battery packs serving as a heating power supply. The main components of the black powder were measured as shown in table 4.
TABLE 4
Composition of Cobalt Lithium ion source Aluminium Copper (Cu) Graphite
Content% 36.6 4.4 3.2 7.7 13.3
2. Selective hot leaching: 400g of black powder is put into a long cylinder (the bottom is provided with a filter screen) decorated by acid-proof polytetrafluoroethylene, a 19V battery pack is connected with a heater to heat acetic acid to about 87 ℃, 26.6 wt% of formic acid (containing 7.3 wt% of sodium thiosulfate) is poured into the long cylinder, hot pouring and soaking are carried out under stirring, 3.6L of formic acid is continuously poured and soaked until the solid in the container is not reduced, 3.6L of formic acid is consumed, 3.4L of first leaching solution under the container is obtained through filtering by the filter screen (the components of the first leaching solution are measured to be 40.7g/L of cobalt, 4.99g/L of lithium, 0.47g/L of aluminum and 0.72g/L of copper, the leaching rate of cobalt is calculated to be 94.5%, the leaching rate of aluminum is 12.5%, the leaching rate of copper is 7.3%), slag in the container is leached, the 19V battery pack is connected with the heater to heat sulfuric acid to about 85 ℃, 7.9 wt% of sulfuric acid is added into the slag to continue hot pouring and leaching until the slag is not reduced, consuming 0.5L of sulfuric acid, filtering by a filter screen to obtain graphite and a second leaching solution, adding 11g of aluminum powder into the second leaching solution, separating to obtain sponge copper, adding 0.15mol/L of sodium hydroxide (containing 10.1 wt% of sodium carbonate) to regulate the pH value of the second leaching solution to 6.2, and performing filter pressing to obtain 63.8g of aluminum hydroxide.
3. Extracting and preparing cobalt oxalate: adding 0.15mol/L sodium hydroxide (containing 10.1 wt% of sodium carbonate) into the first leaching solution to control the pH value to be 6.3, separating to obtain precipitate 4.6g of aluminum hydroxide, adding 14.1 wt% of sulfuric acid to control the pH value to be 3.6, adding a novel synergistic agent (dialkyl hypophosphorous acid: 2-ethylhexyl phosphate mono-2-ethylhexyl: cyclohexane 1.5: 2.5: 8, mixing, adding 0.15mol/L sodium hydroxide, saponifying by 50%), extracting, mixing, oscillating at 60 ℃ in an oscillating box for 30min, standing for 12min, separating to obtain a cobalt-containing phase, adding 7.1 wt% of sulfuric acid, back-extracting, separating to obtain a back-extraction solution, adding sodium oxalate into the back-extraction solution until no precipitate is generated, performing solid-liquid separation, washing and drying to obtain 339g of battery-grade light red cobalt oxalate.
Example 5
A method for recovering waste lithium cobalt oxide batteries comprises the following specific processes:
1. and (4) classification: splitting a waste power battery pack (group) into monomers, detecting according to the residual output voltage of the monomers, measuring and classifying to obtain a first waste power battery (less than 2.5V) and a second waste power battery (more than or equal to 2.5V), conveying the first waste power battery into a bucket containing tap water discharge liquid, soaking for 5d, discharging, conveying to a kiln for pyrolysis at 650 ℃ for about 12h, cooling, crushing, screening to remove copper aluminum foil and diaphragm to obtain black powder; and connecting 6 second waste power battery monomers in series to obtain a single-string 19V battery pack, connecting 4 second waste power battery monomers in series and parallel, connecting a circuit protection plate, and sleeving a fire-resistant film to obtain 6-string 4-parallel 19V battery packs serving as a heating power supply. The main components of the black powder were measured as shown in table 5.
TABLE 5
Composition of Cobalt Lithium ion source Aluminium Copper (Cu) Graphite
Content% 36.6 4.4 3.2 7.7 13.3
2. Selective hot leaching: 400g of black powder is put into a long cylinder (the bottom is provided with a filter screen) decorated by acid-proof polytetrafluoroethylene, a 19V battery pack is connected with a heater to heat acetic acid to about 95 ℃, 26.6 wt% of formic acid (containing 7.3 wt% of sodium thiosulfate) is poured into the long cylinder, hot pouring and soaking are carried out under stirring, 3.2L of formic acid is continuously poured and soaked until the solid in the container is not reduced, 3.1L of first leaching solution under the container is obtained through filtering by the filter screen (the components of the first leaching solution are measured to be 45.9g/L of cobalt, 6.0g/L of lithium, 0.65g/L of aluminum and 0.95g/L of copper, the leaching rate of cobalt is calculated to be 97.2%, the leaching rate of aluminum is 15.7% and the leaching rate of copper is 10.5%), slag in the container is leached, the 19V battery pack is connected with the heater to heat sulfuric acid to about 95 ℃, 7.7 wt% of sulfuric acid is added into the slag to continue hot pouring and leaching until the slag in the container is not reduced, consuming 0.4L of sulfuric acid, filtering by a filter screen to obtain graphite and a second leaching solution, adding 12g of aluminum powder into the second leaching solution, separating to obtain sponge copper, adding 0.15mol/L of sodium hydroxide (containing 10.1 wt% of sodium carbonate) to regulate the pH value of the second leaching solution to 6.1, and performing filter pressing to obtain 65.3g of aluminum hydroxide.
3. Extracting and preparing cobalt oxalate: adding 0.15mol/L sodium hydroxide (containing 10.1 wt% of sodium carbonate) into the first leaching solution to control the pH value to be 6.3, separating to obtain precipitate 4.7g of aluminum hydroxide, adding 14.1 wt% of sulfuric acid to control the pH value to be 3.5, adding a novel synergistic agent (dialkyl hypophosphorous acid: 2-ethylhexyl phosphate mono-2-ethylhexyl: cyclohexane 1.5: 3.5: 9, mixing, adding 0.15mol/L sodium hydroxide, saponifying by 50%), extracting, mixing, oscillating at 60 ℃ in an oscillating box for 30min, standing for 12min, separating to obtain a cobalt-containing phase, adding 7.1 wt% of sulfuric acid, back-extracting, separating to obtain a back-extraction solution, adding sodium oxalate into the back-extraction solution until no precipitate is generated, performing solid-liquid separation, washing and drying to obtain 348g of battery-grade light red cobalt oxalate.
Table 6 examples 1-5 cobalt oxalate with cobalt and other impurity levels
Examples Cobalt/%) Copper/% of Aluminum/%) Sodium/%) Iron%
Example 1 31.54 0.00031 0.000071 0.00023 0.00034
Example 2 31.59 0.00024 0.000077 0.00018 0.00031
Example 3 31.54 0.00037 0.00074 0.00021 0.00037
Example 4 31.63 0.00030 0.00060 0.00017 0.00052
Example 5 31.66 0.00034 0.00064 0.00016 0.00053
As shown in Table 6, the cobalt oxalate prepared in the examples 1-5 has a cobalt content of 31.5%, copper of 0.0008%, aluminum of 0.001%, sodium of 0.001% and iron of 0.001%, and the purity completely meets the requirement of battery grade cobalt oxalate in GB/T26005-2010, which shows that the co-extractant of the present invention has high selectivity for cobalt and excellent extraction effect.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (10)

1. A method for recovering waste lithium cobalt oxide batteries is characterized by comprising the following steps:
s1: filling black cobalt acid lithium battery powder into a column-shaped container, adding a first acid into the column-shaped container for hot leaching until the solid in the column-shaped container is not reduced any more, so as to obtain a first leaching solution and leaching residues, wherein the first acid is a weak acid, and the bottom of the column-shaped container is provided with a filtering structure;
s2: and adding a second acid into the column-shaped container filled with the leaching residues for hot leaching until the solid in the column-shaped container is not reduced any more, so as to obtain a second leaching solution and graphite, wherein the second acid is a strong acid.
2. The recycling method according to claim 1, wherein in step S1, the lithium cobaltate battery black powder is obtained by the following steps: splitting a waste lithium cobaltate battery pack into monomers, detecting the voltage of the monomers, classifying the monomers into low-voltage monomers and high-voltage monomers, discharging, pyrolyzing and crushing the low-voltage monomers, and screening to remove copper aluminum foils and diaphragms to obtain the lithium cobaltate battery black powder.
3. The recycling method according to claim 2, wherein the high voltage cells are assembled into a battery pack as a heating power source.
4. The recovery method according to claim 1, further comprising a step of preparing cobalt oxalate from the first leachate: adding alkali into the first leaching solution to adjust the pH value, separating out aluminum hydroxide precipitate, adding the second acid to adjust the pH value to 3.0-4.5, adding a co-extractant to perform extraction, separating out a cobalt-containing phase, adding the second acid into the cobalt-containing phase to perform back extraction, separating to obtain a back extraction solution, adding an oxalic acid source into the back extraction solution, and performing solid-liquid separation to obtain the cobalt oxalate.
5. The recycling method according to claim 1, wherein in step S2, the second leachate is first added with aluminum powder to separate sponge copper, and then added with alkali to adjust the pH to 4.0-6.5 to separate aluminum hydroxide.
6. The recovery method according to claim 1, wherein in step S1, the first acid is at least one of formic acid, acetic acid, or benzoic acid; the acid content of the first acid is 0.1-35 wt%.
7. The recovery method according to claim 1, wherein the temperature of the first acid is 35 to 80 ℃ in step S1; the first acid also contains sodium thiosulfate, and the content of the sodium thiosulfate is 0.1-12 wt%.
8. The recovery method according to claim 1, wherein in step S2, the second acid is at least one of hydrochloric acid, phosphoric acid, sulfuric acid, or nitric acid; the concentration of the second acid is 0.01-0.2 mol/L; the temperature of the second acid is 35-80 ℃.
9. The recovery method according to claim 4, wherein the synergistic agent is prepared from the following components in a mass ratio of (15-50): (30-85) and cyclohexane, wherein the extracting agent is prepared from the following components in a volume ratio of (1-4): (1-10) dialkylphosphinic acid and 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester.
10. The recycling method according to claim 4, wherein the oxalic acid source is at least one of oxalic acid, ammonium oxalate or sodium oxalate.
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